THOMAS J. KATZAND PETERJ. GARRATT
4876
-oil at room temperature and had infrared and proton magnetic resonance spectra consistent with a compound of this structure. Anal. Calcd. for C21H1504C1: 68.76; H, 4.09; mol. wt., 366.5. Found: C, 68.42; H, 4.06; mol. wt., 366.4. T h e molecular weight was determined on the Mechrolab Model 301 vapor pressure osmometer using chloroform as the solvent. 0,O'-Dibenzoyldihydroxyphenylmethane (19i) was synthesized using a procedure identical with t h a t of 19j with comparable yields, m.p. 61.5-62.5", lit.8 m . p . 62-63'.
c,
[CONTRIBUTION FROM THE
DEPARTMENT OF
Vol. 86
Acknowledgments.-We gratefully acknowledge the help of &Tonsanto Chemical Company for the Summer fellowships Of and lgG3and E' I' du de Nemours and Company for the fellowship grant for the fall semester of 1963. We also would like to express Our thanks' to F. M. .' for their contribution of samples of m-chloroperoxybenzoic acid.
CHEMISTRY, COLUMBIA UNIVERSITY,
NEW YORK, N. Y . 10027]
The Reaction of the Cyclooctatetraenyl Dianion with gem-Dihalides. The Addition of Alkyl Carbenes to Cyclooctatetraene B Y THOMAS J. KATZA N D
PETER
J. GARRATT
RECEIVED J U N E 13, 1964 Dipotassium or dilithium cyclooctatetraenide reacts with 1,l-dichloroethane to yield syn-9-methylbicyclo[6.1.0]nonatriene (11) and with l,l,l-trichloroethane t o yield 9-chloro-9-methylbicyclo[6.1.0]nonatriene. A mixture of cyclooctatetraene and methylene chloride reacts with methyllithium containing lithium iodide t o give 11 in low yield and with methyllithium containing lithium bromide to give some 11, but mainly synand anti-9-chlorobicyclo[6 l.O]nonatriene (Ia and b ) . ( T h e predominant syn isomer, Ia, is isolated.)
Introduction Mixtures of methylene chloride, methyl- or n-butyllithium in ether, and any of a number of olefins react to form chlorocyclopropanes,l apparently through the intermediate divalent carbon species* chlorocarbene, which adds to the olefin to yield the observed product. Accompanying this reaction is a side reaction in which n-butyllithium, for example, combines with methylene chloride to yield 1-pentene, apparently through the intermediacy of an alkyl carbene (eq. 1). C4HgLi
CHzClz ___) CHCl
CaHsLi
C4HoCHLiCI (1)
C~H,CH=CH~+C,H$H
However, one product normally not observed is the alkylcyclopropane that would form if the alkylcarbene added to the olefin. Presumably this reaction cannot compete with others that the alkylcarbenes might undergo, such as intramolecular rearrangement to yield olefins or internal insertion to yield cyclopropanes. It is observed t h a t olefins and, cyclopropanes form in numerous reactions t h a t appear to proceed through the intermediacy of alkylcarbenes*- the reaction of alkyllithiums with methylene ~ h l o r i d e ,the ~ thermal decomposition of salts of toluenesulfonylhydrazones, the thermolysis or photolysis of d i a ~ o a l k a n e sthe , ~ dehydrohalogenation of alkyl halides,6 and the reduction of gem-dihalides7- in a reaction that is rapid, for the lifetime of ethylidene formed in the vapor-phase photolysis (1) G. I,, Closs and I.. E , Closs, J . A m . Chem. Soc., 81, 5723 (1960). (2) J . Hine, "Ilivalent Carbon," T h e Ronald Press, New York, pu'. Y., 1964. (3) G. I,. Closs, J . A m . Chem. Soc.. 84, 809 (1962). ( 4 ) ( a ) 1,. Friedman and H . Schechter. ibid., 81, 5512 (1959); 81, 1002 (1960), ( h ) J. W . Powell and M. C . Whiting, Tetrahedron, 7, 305 (1959). (5) ( a ) H M . F r e y and I . I). K . Stevens J . A m . Chem. Soc., 84, 2647 ( 1 9 6 2 ) : (b) H . VI. F r e y . Chem. I n n . ( L o n d o n ) , 218 (1962). (6) ( a ) W. Kirmse and W. von E. Doering, Tetrahedron, 11, 266 (1960); (b) I,. Friedman and J . G . Berger, J A m . Chem. Soc.. 83, 492, 500 (1961), ( c ) P. S . Skell and A . P. Krapcho, ibid., 83, 754 (19fil). ( 7 ) (a) W. Kirmse. Angew. Chem., 74, 183 (1962); ( h ) W. R. Moore, H I
